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Before you start it would be helpful to… Recall the definition of a covalent bond Be able to balance simple equations Be able to write out structures for hydrocarbons and their derivatives Understand the different types of bond fission Recall the chemical properties of alkanes, alkenes and alcohols THE CHEMISTRY OF HALOGENOALKANES

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STRUCTURE OF HALOGENOALKANES Format Contain the functional group C-X where X is a halogen (F,Cl,Br or I) Halogenoalkanes - halogen is attached to an aliphatic skeleton - alkyl group Haloarenes - halogen is attached directly to a benzene (aromatic) ring

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STRUCTURE OF HALOGENOALKANES Format Contain the functional group C-X where X is a halogen (F,Cl,Br or I) Halogenoalkanes - halogen is attached to an aliphatic skeleton - alkyl group Haloarenes - halogen is attached directly to a benzene (aromatic) ring Structural difference Halogenoalkanes are classified according to the environment of the halogen PRIMARY 1° SECONDARY 2° TERTIARY 3°

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STRUCTURAL ISOMERISM IN HALOGENOALKANES Different structures are possible due to... Different positions for the halogen and branching of the carbon chain 2-chlorobutane 2-chloro-2-methylpropane 1-chlorobutane 1-chloro-2-methylpropane

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NUCLEOPHILIC SUBSTITUTION Theory halogens have a greater electronegativity than carbon electronegativity is the ability to attract the shared pair in a covalent bond a dipole is induced in the C-X bond and it becomes polar the carbon is thus open to attack by nucleophiles nucleophile means ‘liking positive’ the greater electronegativity of the halogen attracts the shared pair of electrons so it becomes slightly negative; the bond is now polar.

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NUCLEOPHILIC SUBSTITUTION Theory halogens have a greater electronegativity than carbon electronegativity is the ability to attract the shared pair in a covalent bond a dipole is induced in the C-X bond and it becomes polar the carbon is thus open to attack by nucleophiles nucleophile means ‘liking positive’ the greater electronegativity of the halogen attracts the shared pair of electrons so it becomes slightly negative; the bond is now polar. NUCLEOPHILES ELECTRON PAIR DONORS possess at least one LONE PAIR of electrons don’t have to possess a negative charge are attracted to the slightly positive (electron deficient) carbon examples are OH¯, CN¯, NH 3 and H 2 O (water is a poor nucleophile) OH¯ CN¯ NH 3 H 2 O

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NUCLEOPHILIC SUBSTITUTION - MECHANISM the nucleophile uses its lone pair to provide the electrons for a new bond the halogen is displaced - carbon can only have 8 electrons in its outer shell the result is substitution following attack by a nucleophile the mechanism is therefore known as - NUCLEOPHILIC SUBSTITUTION

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NUCLEOPHILIC SUBSTITUTION - MECHANISM the nucleophile uses its lone pair to provide the electrons for a new bond the halogen is displaced - carbon can only have 8 electrons in its outer shell the result is substitution following attack by a nucleophile the mechanism is therefore known as - NUCLEOPHILIC SUBSTITUTION Pointsthe nucleophile has a lone pair of electrons the carbon-halogen bond is polar a ‘curly arrow’ is drawn from the lone pair to the slightly positive carbon atom a ‘curly arrow’ is used to show the movement of a pair of electrons carbon is restricted to 8 electrons in its outer shell - a bond must be broken the polar carbon-halogen bond breaks heterolytically (unevenly) the second ‘curly arrow’ shows the shared pair moving onto the halogen the halogen now has its own electron back plus that from the carbon atom it now becomes a negatively charged halide ion a halide ion (the leaving group) is displaced

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NUCLEOPHILIC SUBSTITUTION - RATE OF REACTION BasicsAn important reaction step is the breaking of the carbon-halogen (C-X) bond The rate of reaction depends on the strength of the C-X bond C-I 238 kJmol -1 weakest - easiest to break C-Br 276 kJmol -1 C-Cl 338 kJmol -1 C-F484 kJmol -1 strongest - hardest to break Experiment Water is a poor nucleophile but it can slowly displace halide ions C 2 H 5 Br(l) + H 2 O(l) ——> C 2 H 5 OH(l) + H + (aq) + Br¯(aq) If aqueous silver nitrate is shaken with a halogenoalkane (they are immiscible) the displaced halide combines with a silver ion to form a precipitate of a silver halide. The weaker the C-X bond the quicker the precipitate appears. Advanced This form of nucleophilic substitution is known as S N 2; it is a bimolecular process. work An alternative method involves the initial breaking of the C-X bond to form a carbocation, or carbonium ion, (a unimolecular process - S N 1 mechanism), which is then attacked by the nucleophile. S N 1 is favoured for tertiary haloalkanes where there is steric hindrance to the attack and a more stable tertiary, 3°, carbocation intermediate is formed.

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NUCLEOPHILIC SUBSTITUTION WATER Details A similar reaction to that with OH¯ takes place with water. It is slower as water is a poor nucleophile. EquationC 2 H 5 Br(l) + H 2 O(l) ——> C 2 H 5 OH(l) + HBr(aq)

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ELIMINATION v. SUBSTITUTION The products of reactions between haloalkanes and OH¯ are influenced by the solvent SOLVENT ROLE OF OH – MECHANISMPRODUCT WATERNUCLEOPHILESUBSTITUTIONALCOHOL BASEELIMINATIONALKENE Modes of attack Aqueous solnOH¯ attacks the slightly positive carbon bonded to the halogen. OH¯ acts as a nucleophile Alcoholic solnOH¯ attacks one of the hydrogen atoms on a carbon atom adjacent the carbon bonded to the halogen. OH¯ acts as a base (A BASE IS A PROTON ACCEPTOR) Both reactions take place at the same time but by varying the solvent you can influence which mechanism dominates.

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ELIMINATION ReagentAlcoholic sodium (or potassium) hydroxide ConditionsReflux in alcoholic solution ProductAlkene MechanismElimination EquationC 3 H 7 Br + NaOH(alc) ——> C 3 H 6 + H 2 O + NaBr Mechanism the OH¯ ion acts as a base and picks up a proton the proton comes from a carbon atom next to that bonded to the halogen the electron pair left moves to form a second bond between the carbon atoms the halogen is displaced overall there is ELIMINATION of HBr. Complication With unsymmetrical halogenoalkanes, you can get mixture of products

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ELIMINATION ANIMATED MECHANISM

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ELIMINATION Complication The OH¯ removes a proton from a carbon atom adjacent the C bearing the halogen. If there had been another carbon atom on the other side of the C-Halogen bond, its hydrogen(s) would also be open to attack. If the haloalkane is unsymmetrical (e.g. 2- bromobutane) a mixture of isomeric alkene products is obtained. but-1-ene but-2-ene can exist as cis and trans isomers

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USES OF HALOGENOALKANES SyntheticThe reactivity of the C-X bond means that halogenoalkanes play an important part in synthetic organic chemistry. The halogen can be replaced by a variety of groups via nucleophilic substitution.